US4747931A - Composition and method for coke retardant during pyrolytic hydrocarbon processing - Google Patents
Composition and method for coke retardant during pyrolytic hydrocarbon processing Download PDFInfo
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- US4747931A US4747931A US07/047,740 US4774087A US4747931A US 4747931 A US4747931 A US 4747931A US 4774087 A US4774087 A US 4774087A US 4747931 A US4747931 A US 4747931A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B43/00—Preventing or removing incrustations
- C10B43/14—Preventing incrustations
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the eroionite or offretite type, e.g. zeolite T
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/86—Borosilicates; Aluminoborosilicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/88—Ferrosilicates; Ferroaluminosilicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/949—Miscellaneous considerations
- Y10S585/95—Prevention or removal of corrosion or solid deposits
Definitions
- the present invention is directed to a method and composition for use in inhibiting the formation and deposition of coke on surfaces during the elevated temperature processing of hydrocarbons.
- Coke deposition is generally experienced when hydrocarbon liquids and vapors contact the hot metal surfaces of the processing equipment. While perhaps not entirely technically understood, because of the complex makeup of the hydrocarbons, the hydrocarbons at elevated temperatures and in contact with hot metallic surfaces undergo various changes through either chemical reactions and/or decomposition of various unstable components of the hydrocarbon.
- the undesired products in many instances include coke, polymerized products, deposited impurities and the like. Whatever the undesired product that may be formed, the result is the smae, i.e., reduced economies of the process. If these deposits are allowed to remain unchecked, heat transfer, throughout and overall productivity are detrimentally effected. Moreover, downtime is likely to be encountered due to the necessity of either replacing and/or cleaning of the affected parts of the processing system.
- Feedstocks now include light naphtha, heavy naphtha and gas oil.
- the feedstocks are cracked generally in the presence of steam in tubular pyrolysis furnaces.
- the feedstock is preheated, diluted with steam and the mixture heated in the pyrolysis furnace to about 1500° F. and above, most often in the range of 1500° to 1650° F.
- the effluent from the furnace is rapidly quenched by direct means or in exchangers which are used to generate high pressure steam at 400 to 800 psig for process use. This rapid quench reduces the loss of olefins by minimizing secondary ractions.
- the cooled gas then passes to the prefractionator where it is cooled by circulating oil streams to remove the fuel oil fraction.
- the gas leaving the quench exchanger is further cooled with oil before entering the prefractionator.
- the heat picked up by the circulating oil streams is used to generate steam and to heat other process streams.
- the mixture of gas and steam leaving the prefractionator is further cooled in order to condense the steam and most of the gasoline product in order to provide reflux for the prefractionator. Either a direct water quench or heat exchangers are used for this cooling duty.
- 4,105,540 and 4,116,812 are generally directed to fouling problems in general, the patents disclose the use of certain phsophate and phosphate and sulfur containing additives for use purportedly to reduce coke formation in addition to general foulants at high temperatue processing conditions.
- French Pat. No. 2,202,930 (Chem. Abstracts Vol. 83, 30687K) is directed to tubular furnace cracking of hydrocarbons where molten oxides or salts of group III, IV or VIII metals (e.g., molten lead containing a mixture of K 3 VO 4 , SiO 2 and NiO) are added to a pretested charge of, for example, naphtha/steam at 932° F. This treatment is stated as having reduced deposit and coke formation in the cracking section of the furnace.
- molten oxides or salts of group III, IV or VIII metals e.g., molten lead containing a mixture of K 3 VO 4 , SiO 2 and NiO
- the invention entails the use of certain boron compounds, and compositions containing such, to inhibit the formation and deposition of coke on metallic surfaces in contact with a hydrocarbon (either in liquid or gaseous form) which surfaces reach temeratures of 1400° F. (or 1450° F.) and above most often 1500°-2050° F.). These temperatures are commonly encountered as earlier indicated in the olefin plants. In these systems the components of the furnace (pyrolytic) as well as the ancillary parts are composed of ferrous metal.
- Iron, as well as iron alloys such as low and high carbon steel, and nickel-chromium-iron alloys are customarily used for the production of hydrocarbon processing equipment such as furnaces, transmission lines, reactors, heat exchangers, separation columns, fractionators, and the like.
- the present inventor discovered that coking during the high temperatures cracking of hydrocarbons may be significantly reduced on the iron based and nickel-based surfaces of processing equipment by adding to the hydrocarbon feed stock or charge before and/or during cracking, ammonium borates and in particular ammonium pentaborates and biborates or compositions containing such.
- ammonium borates are effective when formulated with glycollic-type solvents, in particular ethylene glycol, propylene glycol and the like since they produce marketable and easily fed solutions. Aqueous solutions or simply water solutions of the ammonium borates are also effective.
- ammonium borate compounds may be dissolved in the water or the glycol carriers in any proportions, to produce a product which will provide the necessary amount of boron to any coke-formation prone environment to effectively eliminate or in the least minimize such. Coking is a significant problem and if left untreated will eventually shut the operation down. Accordingly it would be desirable to assure that any product used is either high in boron content or if not high in boron content is fed to the charge at high dosage rates to assure the availability of boron. Accordingly, product formulation lends itself to great flexibility.
- the product can contain on a weight basis from about 1 to 50% ammonium borate, with the remainder being the carrier, for example ethylene glycol.
- the carrier for example ethylene glycol.
- various stabilizing agents may also be added to the formulation as well as any preservative which might be desirable.
- the treatment dosages again are dependent upon the severity of the coking problem, location of such, and of course, the amount of boron based compound in the formulated product. Perhaps the best method of describing the treatment dosage would be based upon the actual amount of "boron" that should be added to the charge. Accordingly the amount of formulated product to be added to a charge should be such to provide 0.1 ppm to 5,000 ppm, and preferably 0.5 ppm to 1000 ppm, of boron to said hydrocarbon charge. When ammonium biborate or pentaborate is added together with the carrier to the hydrocarbon feed stock in 0.1 to 5,000 ppm (B), the borates are present in the combination in an amount of 0.0001 to 2.5% by weight.
- the High Temperature Fouling Apparatus consists of five subsections which together simulate the pyrolysis of gaseous hydrocarbons to make light olefins and the coke formed on the heated metal surfaces during the pyrolysis reaction.
- the feed preheat section is built of 316 stainless steel tubing and fittings and allows the mixing of nitrogen or oxygen containing gas with steam during the bring up and shut down of the HTFA and the propane and steam during the actual test.
- Steam is supplied at 40 psig by a steam generator and nitrogen, oxygen containing gas, or propane from compressed gas cylinders.
- the gases and steam are heated to about 400° F. at which point small amounts of water (blank test) or antifoulant is slowly injected into the stream by a syringe pump.
- the gases flow through a coiled 316SS tube inside an electrically heated furnace.
- the gases are heated to 110°-1200° F. at the furnace exit at a furnace temperature of approximately 1865° F.
- the gases travel through the coker rod assembly.
- This consists of a 316SS rod which is electrically heated to 1500° F. while the gases flow around the heated rod inside a 316SS shell.
- the rod is electrically heated through a silicon controlled rectifier (SCR), then through two 4 to 1 stepdown transformers in series to achieve low voltage (3-4 volts), high amperage (200 amps) heating of the rod.
- SCR silicon controlled rectifier
- a temperature controller is used to achieve power control through the SCR to obtain a 1500° F. rod temperature.
- the gases Upon exiting the coker rod, the gases pass through a condenser coil and then two knock-out flasks in ice baths to remove the water (steam) from the product gases. The remaining entrained water vapor in the gases is removed by passing through drierite.
- the specific gravity of the product gas is determined in a gas densitometer and the gases analyzed using gas chromatography to determine yields. The remaining gases are vented through a safety hood exhaust.
- the furnace was turned on and the temperature thereof was stablized at 1200° F. with the coker rod reaching a temperature of 1500° F. while feeding nitrogen and steam. Oxygen feed containing gas and steam was then commenced and the furnace temperature permitted to increase to about 1450° F. (requiring approximately 10 min.).
- Nitrogen feed which was stopped during the oxygen containing gas feed, was then again initiated, and the rod temperature permitted to decrease to 1200° F. Furnace temperatures were then slowly increased to 1800° F. over a period of 10 min. while the coke inhibitor or water (blank) as the case may be was injected into the mixed gas/steam line prior to the furnace at about 400° F. gas temperature.
- the rod temperature was again increased to 1500° F., then nitrogen feed gradually switched to propane feed (about 2 min.).
- the temperature of furnace was then increased to about 1865° F. over approximately 30 minute period.
- the product gases were analyzed by gas chromatography and the temperatures, flowrates, pressures and product gas gravity recorded every 35 minutes during the 160 min. test on propane/steam feed. Gases exit the furnace tube at about 1150°-1250° F. and exit the coker shell at about 975°-1000° F. temperatures.
- furnace tube and coker shell are cleaned and the coke collected and weighed.
- the coke is burned to determine how much is non-coke (metal corrosion products). After a series of blanks (water) and antifoulant tests are conducted, a steam to coke relationship is determined for the blanks of A/x(condensate rate) and the predicted cokes compared to actual cokes of the treatments to determine percent coke reduction.
- A-B represents the Ansari-Bradley statistical procedure and M-W represents the Mann-Whitney procedure, each of which utilizes its particular manner of developing its particular expression of confidence level.
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Abstract
Description
______________________________________ Percentage by Weight Ingredient Actual Range ______________________________________ Ammonium borate compound 10-15% 1-50 Solvent 90-85% 50-1 ______________________________________
TABLE 1 __________________________________________________________________________ HTFA Data-Decoked Procedure-Propane Feed Boron Containing Coke Retardants Cond. Non- 1 2 Furnace Run Rate, Coke PPM Coke Pred % Additive Solvent Tube No. Ml/Min Gms. B Gms. Coke Prot __________________________________________________________________________ Blank H.sub.2 O 16 5 6.70 .94 0 .07 .91 -3 Blank H.sub.2 O 15 2 8.00 .71 0 .09 .77 7 Blank H.sub.2 O 16 6 6.00 1.15 0 .32 1.02 -13 Blank H.sub.2 O 17 2 6.40 2.19 0 .05 .96 -129 Blank H.sub.2 O 17 7 6.45 1.97 0 .06 .95 -107 Blank H.sub.2 O 17 10 7.51 1.07 0 .11 .81 -31 Blank H.sub.2 O 18 2 7.07 .32 0 .06 .87 63 Blank H.sub.2 O 18 12 7.46 .66 0 .05 .82 20 Blank H.sub.2 O 18 15 8.66 1.37 0 .13 .71 -94 Blank H.sub.2 O 18 20 7.01 .55 0 .06 .87 37 Blank H.sub.2 O 18 25 5.18 .43 0 .08 1.18 63 Blank H.sub.2 O 19 2 6.55 .74 0 .20 .93 21 Blank H.sub.2 O 19 8 6.43 .55 0 .12 .95 42 Blank H.sub.2 O 19 13 8.64 1.14 0 .24 .71 -61 Blank H.sub.2 O 19 19 9.22 .14 0 .07 .66 79 Blank H.sub.2 O 19 20 7.88 .38 0 .11 .78 51 Blank H.sub.2 O 19 27 4.13 2.74 0 .28 1.48 -85 Blank H.sub.2 O 20 2 10.09 .73 0 .08 .61 -20 Blank H.sub.2 O 20 8 7.95 .77 0 .04 .77 0 Blank H.sub.2 O 20 14 10.55 .71 0 .23 .58 -22 Blank H.sub.2 O 20 20 8.72 .21 0 .26 .70 70 Blank H.sub.2 O 21 2 6.95 .20 0 .05 .88 77 Blank H.sub.2 O 21 3 5.82 .49 0 .06 1.05 53 Blank H.sub.2 O 21 7 8.64 .52 0 .04 .71 27 Blank H.sub.2 O 21 13 7.33 .77 0 .11 .83 8 Blank H.sub.2 O 21 20 8.48 .44 0 .12 .72 39 Blank H.sub.2 O 22 8 7.39 .74 0 .23 .83 11 Blank H.sub. 2 O 22 14 7.64 .74 0 .31 .80 8 Blank H.sub.2 O 22 20 8.72 .37 0 .48 .70 47 (NH.sub.4)2B10016 14.5%/EG 17 5 7.70 .78 71 .05 .79 2 (NH.sub.4)2B10016 15%/EG 18 8 7.40 .98 45 .09 .83 -18 (NH.sub.4)2B10016 15%/EG 18 13 7.59 .24 44 .05 .81 70 (NH.sub.4)2B10016 15%/EG 18 21 8.48 .17 44 .06 .72 76 (NH.sub.4)2B10016 10%/H.sub.2 O 21 18 9.59 .31 27 .06 .64 51 (NH.sub.4)2B10016 10%/H.sub.2 O 22 13 8.48 .28 27 .11 .72 61a (NH.sub.4)2B407 15%/EG 18 9 8.24 .63 38 .05 .74 15 (NH.sub.4)2B407 15%/EG 18 24 9.42 .15 37 .04 .65 77 (NH.sub.4)2B407 15%/EG 19 14 9.65 .41 36 .10 .63 35 (NH.sub.4)2B407 10%/EG 19 22 8.83 .18 24 .12 .69 74 (NH.sub.4)2B407 10%/EG 20 4 10.25 .46 22 1.33 .60 23 (NH.sub.4)2B407 10%/EG 20 6 9.62 .29 24 .22 .64 54 (NH.sub.4)2B407 10%/EG 21 19 8.38 .52 25 .22 .73 29 (NH.sub.4)2B407 10%/H.sub.2 O 20 5 8.36 .39 24 .18 .73 47 (NH.sub.4)2B407 10%/H.sub.2 O 20 7 8.04 .39 23 .07 .76 49 (NH.sub.4)2B407 10%/H.sub.2 O 21 4 9.56 .82 22 .19 .64 -28 (NH.sub.4)2B407 10%/H.sub.2 O 21 21 8.58 .29 22 .06 .71 59 (NH.sub.4)2B407 10% in H.sub.2 O/ 20 9 7.54 .40 22 .06 .81 51 EG(3) (NH.sub.4)2B407 10% in H.sub.2 O/ 22 15 8.15 .76 23 .46 .75 -1 EG(3) __________________________________________________________________________ 1 Predicted coke = 6.12/condensate rate (ml/min) 2 (1coke/predicted coke) × 100% EG Ethylene Glycol a Partially plugged coke inhibitor feed line (3) Ratio of H.sub.2 O/EG is 3:1
TABLE 2 __________________________________________________________________________ Summary of HTFA Results on Boron Antifoulants # of Coke Protection % Statistical Analysis Additive Runs Range Avg. SD Median A-B (SL)* M-W (#/CV)** __________________________________________________________________________ Blank/H.sub.2 O 29 -129/79 5.2 56 11 -- -- (NH.sub.4)2B10016 6 -18/76 40 39 56 .239 120.5/126 (NH.sub.4)2B407 13 -28/77 37 30 47 .047 254/250 __________________________________________________________________________ *Significance level (0.05 is 95% confidence level additive protection is greater than blank protection). **Calculated number vs. critical value for 95% confidence additive protection greater than blank protection.
Claims (6)
Priority Applications (1)
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US07/047,740 US4747931A (en) | 1985-09-06 | 1987-05-08 | Composition and method for coke retardant during pyrolytic hydrocarbon processing |
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US06/773,402 US4680421A (en) | 1985-09-06 | 1985-09-06 | Composition and method for coke retardant during pyrolytic hydrocarbon processing |
US07/047,740 US4747931A (en) | 1985-09-06 | 1987-05-08 | Composition and method for coke retardant during pyrolytic hydrocarbon processing |
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US06/773,402 Division US4680421A (en) | 1985-09-06 | 1985-09-06 | Composition and method for coke retardant during pyrolytic hydrocarbon processing |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4889614A (en) * | 1989-05-09 | 1989-12-26 | Betz Laboratories, Inc. | Methods for retarding coke formation during pyrolytic hydrocarbon processing |
US4962264A (en) * | 1989-10-23 | 1990-10-09 | Betz Laboratories, Inc. | Methods for retarding coke formation during pyrolytic hydrocarbon processing |
US5000836A (en) * | 1989-09-26 | 1991-03-19 | Betz Laboratories, Inc. | Method and composition for retarding coke formation during pyrolytic hydrocarbon processing |
US5258113A (en) * | 1991-02-04 | 1993-11-02 | Mobil Oil Corporation | Process for reducing FCC transfer line coking |
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US4374033A (en) * | 1981-06-18 | 1983-02-15 | Edwin Cooper, Inc. | Dispersant and lubricating oil containing the dispersant |
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US4514326A (en) * | 1978-07-24 | 1985-04-30 | Sallay Stephen I | Permanent flame retardant and anti-smoldering compositions |
US4680421A (en) * | 1985-09-06 | 1987-07-14 | Betz Laboratories, Inc. | Composition and method for coke retardant during pyrolytic hydrocarbon processing |
-
1987
- 1987-05-08 US US07/047,740 patent/US4747931A/en not_active Expired - Lifetime
Patent Citations (9)
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US2960437A (en) * | 1954-09-03 | 1960-11-15 | Pfizer & Co C | Ion exchange purification of basic antibiotics |
US2914481A (en) * | 1956-05-23 | 1959-11-24 | Du Pont | Single phase liquid lubricating, anticorrosion, anti-acid composition and preparation of same |
US3475496A (en) * | 1965-02-22 | 1969-10-28 | Montedison Spa | Process for preparing br3-type organoboron compounds |
US4196177A (en) * | 1978-07-24 | 1980-04-01 | Sallay Stephen I | Process for producing boron compounds from borate ores |
US4382025A (en) * | 1978-07-24 | 1983-05-03 | Sallay Stephen I | Ammoniumtriborate, an effective new flame retardant |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4889614A (en) * | 1989-05-09 | 1989-12-26 | Betz Laboratories, Inc. | Methods for retarding coke formation during pyrolytic hydrocarbon processing |
US5000836A (en) * | 1989-09-26 | 1991-03-19 | Betz Laboratories, Inc. | Method and composition for retarding coke formation during pyrolytic hydrocarbon processing |
US4962264A (en) * | 1989-10-23 | 1990-10-09 | Betz Laboratories, Inc. | Methods for retarding coke formation during pyrolytic hydrocarbon processing |
US5258113A (en) * | 1991-02-04 | 1993-11-02 | Mobil Oil Corporation | Process for reducing FCC transfer line coking |
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